Polymerization process



United States Patent B L E IZ TIQN PRQCESS Milton A. Taves, Wilmington, Del., assignor to'H'ercules Powder Gompany, Wilmington, Del, a corporationcf Delaware- No, Drawing, Application September 15, 19.53., Serial Bio-$80,344

19 Claims. ((31. 260 -825) This invention relates to. animproved process for the polymerization of unsaturated compounds and more-particularly to a process for the emulsion polymerization of vinyl, vinylidene, and vinylene compounds at temperatur s. bslow C..

he emul icnp lym riz on. f viny ompo nds ha customarily been effected at relatively high, temperatures. For example, a temperature, of about 122'" F; has-been acceptedas astandard for the commercialjproduction ot thebutadienQ-SIYrene copolymer-type, synthetic. rubbers. These prior art emulsion polymerization,processes. are, hQWQvenrot asadvantageous in some, respects. as. are polymerizations carried out at lower temperatures. It is known, for example, that the synthetic rubberlike materials produced by emulsion,polymerization at temperatures substantially-below, 122 F. are markedly superior in important physical characteristics such as tensile strength, elongation, fiexlife; resilienee'a-nd resistance to accelerated aging to similar materials prepared within the conventional temperatureranges.

One of the problems which has heretofore hampered the-.cemmercialp oduction f syn hetic rubberlike mae .s.;:by he lcwt mpera rem on polymerization of vinyl compounds has been that of reducing thei reaction imatmau re i .to p oduce: a desirable yield i 015 po ym materi, While; ne: ins an e ese: di-flicalti were Qv rccme at; lea t partially. by he. ti iz i n f a,- mpre. .ac iverinitiat ng.agen it was: usua y f undz necr essary in. eachicasehtohresort also tomore' expensive m lsifying-( gent ..thuspmakingthe proeessnna tractive economically; G nsequently, oneiof;thcnmajonp zoblems 0f hfi;3It ,haS,b. 1IO;find: a; process for the lovwtemper-ar ture emulsionpplymerizatiorr of vinyl: compounds; which would-result in, a; good. quality product afiter ra. reasonable reaction time-and :which .would; allow. vthe :use ofi ingredients-cheap enough to render, thetprocess. economically feasible.-

Now .in-aeeordance. with? this invention, .ithas been discovered that the polymerization .of organic :compounds containingtthe.GH2=C 1 group, may be; effected. at .temperatures-below about 10 C; in;aqueous'emulsiomint'the presence of-an; emulsifiying; agent, a. material capable. of formingan'electromotivetcouple having a standardloxidationvreduction; potential. between; about -1 ..0; and; about -..0 :3-;volt-cas .activating-qagent z and .a polycyclohexyl shydroperoxidm of; not. more; than; 3 carborurings. and-fin whichnthehydroperoxy: group is. attached: to. atertia'ry carbontatomt in one. of the carbon rings.

The ,1 standard. toxidationrreduction potential: toe which reference-ismade-herein is thevalue in voltsxof; thezele'ctric'al potential of the couple'in questiondetermined: at 25 CI underapressure of oneatmospherewith solutions of one molal activity-referred to-the-potentiail of the hydrogen-hydrogen ion couple as zero.- The signof the oxidation-reduction potential value is negative when th'e reduced form,of. the .couple is a weaker. reducingagent t aahy rc e 2,776,953 Patented Jan. 5%, 1957 One. of the components of the activating agents used in, this inventionmay be a metallic reducing agent, and the term metallic reducing agent is utilized herein to designate all of those materials which contain metallic atoms and which are capable of acting as reducing agents, i. e., which are capable of donating an electron to other components of the reaction mixture. Thus, there is embraced by the term metallic reducing agent not only the free metallic ions such as the ferrous ion (Fe++) but alsol complexes of such metallic ions such as the ferrous pyrophosphate complex. Likewise included are metallic compounds which are substantially completely insoluble but which nevertheless act as reducing agents such as, for example, nickel hydroxide (Ni(OH)2) which forms the couple Ni(OH)2+20H- Ni0z+ 2HzO+2e'- the standard oxidation-reduction potential of. whichjs. O.5 volt.

The catalysts of this inventionare polycyclohexyl'hydroperoxides, for example, bicyclohexyl hydroperoxide and: tricyclohexyl hydroperoxide, in which the hydroperoxy; group is attached. to a tertiary carbon atom in one of. the cyclohexyl rings. It is preferred to use the hydroperoxides containing not morev than 3' cyclohexyl rings because: the hydrocarbons from which they areprepared are more easily available, but-hydroperoxidesof more than 3-cyclohexyl rings may also be used. One or more or-allofi the carbon rings maycontain substituent groups. These: catalysts may be represented by the structural formulas:

where Rland/orlh and/or R2 may be H,. X,.XO, XzN, Bror C1,. X being an valkyl radical. R, R1 and R2 may be :the same :or difierent. These compounds, when utili zedascatalysts, permit shorterpolymerization reaction times.at-lowtemperatureswithout sacrifice in yield than was. heretofore possible.

The followingexamples are illustrativeof the preparationof polymers by emulsion polymerization in. accordance with thisinvention. The-bicyclohexyl and-tricyclohexylhydroperoxides used intheseexampleswere prepared-by oxidation of bicyclohexane and: tricyclohexane, respectively, at-115. C.-with oxygen in an aqueous systemsrcontaining 0.8% sodium carbonate by-Weight based upon-.theparticular hydrocarbon. By this method, products containing 545% byweighthydroperoxide were obtained, the major impurities being the corresponding hydrocarbons which are inert in the polymerization re action. The hydroperoxides were concentrated before use 'by'va'cuum distillation of part of the hydrocarbon. All parts in the examples relative to the. hydroperoxides are"on"a"l00% basis and all parts represent parts by weight."

and

Example 1 In this and the following examples, copolymers of butadiene-l,3 and styrene were prepared in glass containers. In this example the reaction mixture was formulated from the following ingredients in the proportions indicated.

Bicycohexyl Hydropcroxide Tertiary Mercaptans 1 (Modifier) 0.156. Activator:

Ferrous Sulfate Hoptahydrate 0.09. Potassium Pyrophosphate 0.20. Dextrose Mouohydrate 0.842.

1 A tertiary mercaptan blend composed of C12, C14 a d On tertiary Inercaptans in the ratio of 3:1:1.

The ferrous pyrophosphate activator was prepared under nitrogen by digesting 0.842 part dextrose monohydrate with 0.20 part potassium pyrophosphate in 7.2 parts water for 10 minutes at 90-100 C. The solution was cooled to 50 C. and 0.09 part ferrous sulfate heptahydrate dissolved in 1.6 parts water was added and the solution agitated at 50 C. for 5 minutes. The solution was then cooled rapidly to 30 C., transferred to a tightly capped vessel and stored at C. under nitrogen. The activator was used within 24 hours after preparation.

The potassium salt of dehydrogenated rosin which was employed as an emulsifier was prepared by dissolving the dehydrogenated rosin, trisodium phosphate and potassium hydroxide in 168 parts distilled water and boiling for 2 minutes. The solution was cooled to room temperature and sufficient distilled water to make a total of 177 parts solution was added. The dehydrogenated rosin employed was prepared by dehydrogenating a distilled N wood rosin (about light ends and 8% residue removed) in the presence of a palladium-on-carbon catalyst. The product so obtained had an acid number of 161.

After the emulsifying agent had been prepared, the mercaptan modifier and hydroperoxide were dissolved in freshly washed and dried styrene and the resultant solution charged to a glass reaction vessel along with the emulsifying agent in such a manner that the two phases did not mix. The vessel was sealed and freshly distilled butadiene was added by injection with a hypodermic needle and the vessel stored at 0 C. until the reaction was initiated. Initiation of the reaction was eflected by injecting the activator solution into the reaction vessel. The reaction vessel was then shaken vigorously, pressured with 15 lb. nitrogen and tumbled end over end in a 5 C. bath. Samples of the contents of the reaction Vessel were withdrawn at periodic intervals after the addition of the activator. To each sample so obtained was added a small portion of ditertiary butyl hydroquinone in a small amount of ethanol to prevent further conversion and the sample dried in a low pressure oven at 70-80 C. From the weight of the dried latex, the percent of hydrocarbon conversion was calculated. It was determined that a 60% conversion was obtained in 5.0 hours as compared to 7.1 hours for a diisopropylbenzene monohydroperoxide control and 6.2 hours for a pmenthane hydroperoxide control.

Example 2 The procedure of Example 1 was carried out except that 0.185 part tricyclohexyl hydroperoxide was substituted for the bicyclohexyl hydroperoxide of Example 1. A 60% conversion of monomers to copolymer was obtained in 5.0 hours as compared to 7.1 hours for a diisopropylbenzene monohydroperoxide and 6.2 hours for a p-menthane hydroperoxide control.

Example 3 In this example butadiene and styrene were copolymerized according to the procedure of Example 1 with the exception that in this example a ferrous sequestrene activator was utilized. This activator was prepared by dissolving 0.244 part ethylenedinitrilotetraacetic acid in an equivalent amount of aqueous potassium hydroxide solution and adding thereto a solution of 0.207 part ferrous sulfate in 2.4 parts boiled distilled water at room temperature with stirring under nitrogen. Boiled distilled water in the amount of 2.8 parts was added and the solution was stored in a polymerization vessel under 15 lb. nitrogen pressure until utilized. Bicyclohexyl hydroperoxide in the amount of 0.165 part was utilized in this example. A 60% conversion of monomers to copolymer was obtained in 0.9 hour compared to 1.8 hours for a p-menthane hydroperoxide control.

Example 4 Following the procedure of Example 3, butadiene and styrene are polymerized utilizing 0.233 part tricyclohexyl hydroperoxide in place of bicyclohexyl hydroperoxide. A 60% conversion is obtained in 0.9 hour compared to 1.8 hours for a p-menthane hydroperoxide control.

The polycyclohexyl hydroperoxide catalysts of this invention may be prepared by the oxidation of the corresponding polycyclohexyl compounds. These compounds have the structural formulas wherein R, R1 or R2 may be the same or different groups and may represent H, X, X0, XzN, Br or Cl, where X is an alkyl radical.

The oxidation may be carried out in the liquid phase utilizing air or molecular oxygen as the oxidizing agent. A preferred method of preparing these hydroperoxides involves the oxidation of the corresponding polycyclohexyl compound having one or another of the above structural formulas by passing an oxygen-containing gas through the compound at a temperature between about 50 C. and C. in the presence of an aqueous alkali such as, for example, sodium carbonate. Ultraviolet light may be used to initiate the oxidation reaction. The concentration of the alkali may be between about 0.01% and about 35%, although it is preferable to use concentrations of about 0.01% and about 2%. Vigorous agitation is desirable during the oxidation reaction.

As illustrative of the polycyclohexyl compounds, ofltcr than bicyclohexyl and tricyclohexyl which may be mild ized to hydroperoxides of this invention, alkyl-substituted bicyclohexyl and tricyclohexyl compounds may be mentioned. There may be more than one alkyl group attached to the molecule and all these alkyl groups may be attached to one or another carbon ring or they may be attached to more than one such group. Alky1-substituted bicycloand tricyclo-hexyl compounds in which the alkyl group contains not more than 7 carbon atoms produce, upon oxidation, hydroperoxides which are preferred over similar hydroperoxides containing larger alkyl groups. Alkyl groups containing not more than 7 carbon atoms are referred to herein as lower alkyl groups. Alkyl substituent groups should be saturated.

Illustrative of the alkyl groups mentioned are methyl-, ethyl-, n-propyl-, n-butyl-, isobutyl-, tertiary butyl-, pentamethylethyland the like. As representative of the hydrocarbons which may be oxidized to hydroperoxides of this invention, bicyclohexyl, methylbicyclohexyl, ethylbicyclohexyls, n-propylbicyclohexyl. and.- the. like? may; be mentioned,.. as. may be; the. corresponding; methyl,- ethyl, propyl, butyl, etc. derivatives of tricyclohexyl; Upon oxidation, these hydrocarbons lead to lcyclohexyl-l-ihydmperoxy: cyclohexane, methylelfcyclohexylelehydroperoxy' cyclohexane, aethyl-.1.-cyclohexyl-l-hydroperoxy cyclohexane, n propyl-l-cyclohexyl-lhydroperoxy cycloherane;-..etc., and/correspondingly with similar: alkyl derivatives of tricyclohexyl. It is also possibleito-havamore thanone :substit-uen-tgroup attached; to vone of the -cyc'lohenylzringsa as: in the case: of. l-dimethylcycloh'eXyl-lh'ydnoperoxy cyclohexane; larnethylethylcyclohexyl-lahydr'operoxy cyclohexane:

Likewise; in those-instances .where substituentsrof one 011 more; cyclohexylrings: are: one =:or another. or a combinationiofa XO,.X2'N;. B1. or Cl, where X is an alkyl groumzthe: compoundssuchc as; for example; bromobi cyclohexylg. h romotricyclohexyl'; mayo be-v oxidized to. the conresponding hydroperoxides. Examples of compounds which contain thecalkoxygroup arerrnethoxybicyclohexyl, metlroxytricyclohexyl, etc.v Dialkylamino' substituted polycyclohexyl compounds: which are toperablec are= illustrated by dimethylaminobicyclohexyl; methylethylaminm 'bicycloh'exyl, etcg andrcorresponding derivatives of tri cycloh'exyli I All of-*'th'e= foregoing: compounds andztheirhomologs 'and' equival'ents' maybe oxidized tmpolycyclohexylnhydroperoxides of" this invention; In? each: instance: the 'hydi operoxide which is effective: in. this invention r isva monohydioper-oxide in which i the h-ydroperoxy group: is attached to a tertiarycarbo'n atom inv-one of: the cycle hexyl" rings; While none. of the representative compounds mentioned contain alkylgroupsshavingzmorei than a L few carbon atoms; one skilled in: the; artiwill's realize tliat'higher homologs -rnay also be utilized; However, b'icyclohexylandtricyclohexyl hydroperoxides containing containingdowenalltylsubstituent groups, that'is, polycyclohexyl hiydnoperoxides containing not more." than: 3 cyclohexyl rings and-having substituentgroups' 'whichrare saturatedllower alkyl' radicals of not more .than: 7 "carbon atoms are preferred in this invention; The compounds, bicycloh'exyl hydro-peroxide, tricyclohexylhydnoperoxide, methylbicyclohexyl hydroperoxide; met-hyltricyclohiexyl hydroperoxi'de" and l pentamethylethylcyclohexylil-hydroperoxy"cyclohexane are particularlypreferredilas producing'outstanding results.

Theamount' ofh'ydroperoxide which may ber-used iin accordance with this invention= may bebetween about 011%"andabout 20%" basedon the amount of. solid emulisifying agent usedfi The preferable amount of. hydroper- 'ox'rde on" this basis, however, is from' about .5.%'z.to about-4% Based' on the monomers; the amount :of hyd roperoxide may be from about 0.001 to abouut5;0%, a; desirablerange being from" about. 0;005% to: about l'.0%, and the preferable-amount of hydroperoxidevon this basis being from about 0-.0'l% to" about 012%;

' Tlie'process of this"inve ntion may berca'rried :out' using various emulsifying agents,- such: as fatty"'acidrsoaps; the water soiuble salts of h'ydrogenated and dehydrogenated rosins or of the pure acids thereof,:'such'as-dihydroabietic, tetriahydroabietic,.z. and dehydroabietic acids; the watersoluble salts of the samines derived from: hydrogenated and:fdohydrogenatedirosinsor from thepureacids thereofgifon example the' acetates of dihydroabiethylamine, tetnahydroabiethylamine, and. dehy-droabiethylamin'e; and any ;other,-emulsi-fying. agent Well known in the art. The rosin amines mentioned. may be prepared by converting the-acidsin.theaosin'material to the co-rresponding 'nitril'es by treatment with ammonia under dehydrating conditions, and ..then reducing the nitriles to the amines-'by'catalytic hydrogenation.

: The salts of hydrogenated and dehydrogenatedflrosin which may heused" as emulsifying 1 agents in: this inven+ 't ion-are'prepared by the neutralization; of hydrogenated and d'ehydrogenated-rosin;.respectively, with: an alkali metaleompound. basic in-characteristics, such as the hy,- droxides and carbonates of. sodium and. potassium.- Hydrogenated rosin. acidsoaps and dehydrogenated rosin acidsoapsmay be utilized-Cm conjunction with-fatty acid soaps as emulsifying agents in the process of this inventiont Thus, emulsifying. agents containing up to 50% fattyacid-soapsby weight mayibe utilized. Apreferable range of concentration oftfatty acid. soaps-is from about 10%: to about:30% of the weight ofthe emulsifying agent, It is preferable that the fattytacid soaps employed in this inventicnbeprepared from long-chainv fatty acids which. have. from about l2-to about 18 carbon atomsin the molecule. A readily available source of such a mixture ofafatty acids-and rosin acids is-tall-oil-.- Tall oil is a.by-p-roduct from the manufacture of paper pulp by the digestion ofwoodwith alkaline-liquorssuch asalkal-in'e solutions of sodium sulfide. Crude tall oil:consists-'of a mixture ofrosin' andifatty acids inroughly equal proportionsimconjunction with minor. amounts of neutral, unsaponifia'ble. materialsconsisting: primarily of plant sterols. For utilizationwin :thepreparation of the emulsifyingv agents: of this invention it is desirable thatth'e tall oil.-be.-refi-ned to remove certain' polymerization inhibiti-ng materials by treatment with a spent -hydrogenati'on catalyst-and then hydrogenated or dehydrogenated.

The remulsifying agents -h'ereinbefore described may: be employed Lina an: amount equivalent to from about 0.2% to about 5% basedon' thetotal emulsion polymerization reactionumimturei A" preferred range on this basis is fro'rn-about-'0.5 to about 2% ofthe weight of thereact-iona mixture; The: concentration of the emulsifying agent in the-aqueous phase: may be from about 0 .5% to about 5%; preferably: from: about 1% to about" 3%: B asedvona .the :weight of :the: monomers originally present, the enrulsifyingz-agent may be: utilized in an: amount equiv alentto from'about 0.5 70" to about 15% of'the weight thereof 'andipreferably' 'in' ant-amount equivalent to from about' .2-% to: about. 16%: of the weight thereof.

Tho -activators which areoperable'in: the process ofthis invention comprise those electromotive couples havinga standard oxidation reduction potentialbetween about --l. '0-'and about -0.3 volt, preferably betweeniabout 0'.8to1ab'out 0;5' volt; Such activators I shoul'dflbe capable of reducing a phenylcyclo'h'exyl hydrop'eroxide such" as; for" example, phenylcycloh'exyl' hydroperoxide-itself toa ketone. inub'etter' than about 25% yield in: frDm abDutiOLZS- hour to about 50' hours. Preferable'are t-h'o'se 'elec'trom'otive couples containing a -m'etalilic r'educing' agent," such as the ferrous (F'e++-) ion, which forms a-couple'in the=reaction mixture with an analogous material of higheroxidati'on state, such as-the ferric (Fe++f+') ion.

In sofar as the preparation offerrous pyrophosphate activators is concerned;- the pyr'ophosphate compound and the ferrous salt utilized should be employed in such proportions that there is present in the reaction mixture in which the activator is formed from about 0.3 to about 2.5 chemical equivalents of the pyrophosphate for each chemicaluequivalent of the ferrous salt A preferable range is'fromabout O.8 to.about ZIO'chemic'al equivalents of pyrophosph-ate per chemical equivalent of ferrous salt. Particularlydesirable isth'e presence of about 1.4 chemicalfl equivalents of pyroph'osphate for each chemical equivalent of ferrous salt. Soluble ferrous salts other than ferrous sulfate, such as, for example, ferrous chloride either alone or in combination withoflterreducing agents such as reducing sugars may; of course, be utilized inthe preparation of the ferrous activatorswhich" are operable in the process of this invention; Likewise, similar salts of analogous metals may be employed. It is'desirable, of course, that the metallic ion component of these salts be in a're'duced oxidation state. Furthermore, the ferrous andan'alo'g'ous metallic ionsderivedfrom these-salts may be oomplexed' with anions other than the pyrophosphate ion to form"oper'ab1 activators. For

example, gluconate and citrate ions may be so utilized. The ferrous complex of ethylenedinitrilotetraacetic acid, ferrous-o-phenanthraline and polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine also are operable.

The reducing agents operable in this invention, it will be observed, are essentially characterized by their ability to form an electromotive couple having a standard oxidation-reduction potential of between l.0 and -0.3 volt and it is this electrochemical manifestation of these compounds which is the critical factor in distinguishing the reducing agents of this invention from other reducing agents.

The activator may be used in such an amount that there is provided from about 0.1 to about 3.0 electrons for each hydroperoxy radical. A preferable range for freshly prepared activators is from about 0.8 to about 1.2 electrons per hydroperoxy radical, and that for activators aged at room temperature or by heating for a short time at elevated temperatures is from about 0.8 to about 2.0 electrons per hydroperoxy radical.

Aqueous solutions of water-soluble organic compounds of low freezing point may be employed as antifreeze media when the process of this invention is carried out at sub-zero temperatures. Thus, water solutions of the lower alkanols, such as methanol and ethanol, may be utilized. Also operable are water solutions of other alcohols, including polyfunctional alcohols such as glycerol or ethylene glycol. In fact, at quite low temperatures,

better reaction rates are often obtained by the utilization .1

as antifreeze agents of such polyfunctional molecules. If desired, water solutions of nonalcoholic compounds such as acetone and methyl acetate may be employed. In any particular instance, those skilled in the art will be able to select or formulate a reaction medium, the freezing point of which is below the temperature at which it is desired to effect a particular polymerization reaction. Such reactions may be readily carried out at temperatures of -l5 C. in a medium consisting of 3 parts of water and 1 part methanol. As previously indicated, it is advantageous prior to admixing the emulsifying agent with the other ingredients of the polymerization system to form a solution or suspension thereof in a portion of the antifreeze medium.

or-Hydroxy carbonyl compounds or compounds which react as a-hydroxy carbonyl compounds may be added to the other ingredients of the reaction mixture in the process of this invention. Thus, such compounds as fructose, glucose, lactose, sorbose, acetylacetone, ascorbic acid, benzoin, acetoin, propionoin, butyroin, isobutyroin,

pivaloin and the like may be utilized. In general, those aldehydes and ketones containing a hydroxyl group on an adjacent carbon atom in an alkyl chain and having thereby in common the structural group are operable in this invention. The preferable a-hydroxy aldehydes and ketones are those compounds which are known as reducing sugars. As illustrative of the a-hydroxycarbonyl compounds in general, the amount of reducing sugar employed may vary from about 0.01 to about 6% of the weight of the monomers. A preferable range on this basis is from about 0.1 to about 3%. Particularly appropriate is that quantity of sugar equivalent to about 0.5% of theweight of the monomer.

It is desirable, particularly in the polymerization of those compounds leading to synthetic rubberlike materials, that there be included in the polymerization reaction mixture a modifying agent. The conventional modifying agents may be used in the process of this invention. Thus, the mercaptans normally so employed may be utilized, and the amount may be that usually used, for example, in the preparation of synthetic rubbers. It is desirable, however, that the mercaptan modifier be tertiary for the reason that improved modification of the rubber is thereby obtained. Primary mercaptans may, however, be employed if desired.

The emulsion polymerization of the vinyl, vinylene and vinylidene compounds may be eflfected in accordance with this invention at temperatures up to about 10 C. Temperatures as low as 70 C. may be employed if desired. The preferable temperature range is from about 30 C. to about 10 C.

If desired, small quantities of inorganic salts such as potassium sulfate may be added to the reaction mixture to reduce the viscosity of the latices of the polymers obtained. The utilization of large quantities of such salts, however, adversely affects the range and extent of polymerization. A preferable range of concentration of such salts is from about 0.1 to about 0.5% of the weight of the monomers. Except as otherwise indicated, the conventional emulsion polymerization techniques, concentrations of reactants and reaction conditions may be utilized in practicing the process of this invention.

Any vinyl compound which may be advantageously polymerized by peroxide initiation in an emulsion polymerization process is operable according to the process of this invention. Illustrative of these compounds are the conjugated butadienes such as butadiene-1,3, isoprene, 2,3-dimethyl butadiene-1,3, chloroprene, piperylene, monomer mixtures of two or more of these conjugated butadienes such as a mixture of butadiene-l,3 and 2,3-dimethyl butadiene-1,3 and monomer mixtures of one or more of these conjugated butadienes with vinyl compounds such as styrene, p-chlorostyrene, p-methoxystyrene, vinyl naphthalene, acrylic acid, methacrylonitrile, methyl methacrylate, methyl acrylate, methyl vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether and the like. The process of this invention is particularly applicable to the preparation of the copolymers of butadiene and styrene or acrylonitrile, isoprene and styrene or acrylonitrile, and other rubberlike copolymers as well as in the preparation of polymers such as polyvinyl chloride, polyvinyl acetate, polystyrene, polyrncthylmethacrylate, polyvinylidene chloride, polyvinyl pyridine, and the various other addition polymers which may be prepared by the emulsion technique.

What I claim and desire to protect by Letters Patent is:

1. The process which comprises polymerizing an organic compound containing the CH2=C group at a temperature below about 10 C. in aqueous emulsion in the presence of an emulsifying agent, an electromotive couple having a standard oxidation-reduction potential between about 1.0 and about 0.3 volt as activator and as catalyst a polycyclohexyl hydroperoxide in which the hydroperoxy group is attached to a tertiary carbon atom in a cyclohexyl ring.

2. The process of claim 1 in which the activator is an electromotive couple having a standard oxidation-reduction potential between about 0.8 and 0.5 volt.

3. The process of claim 1 in which the emulsifying agent is potassium dehydroabietate.

4. The process of claim 1 in which butadiene-1,3 and styrene are copolymerized.

5. The process of claim 1 in which the emulsifying agent is potassium tetrahydroabietate.

6. The process of claim 5 in which the hydroperoxide is tricyclohexyl hydroperoxide, the monomers polymerized are butadiene-1,3 and styrene and the activator is an electromotive couple having a standard oxidation-reduction potential between about -0.8 and 0.5 volt.

7. The process of claim 1 in which butadiene-1,3 is polymerized.

8. The process of claim 7 wherein the hydroperoxide is l-cyclohexyl-l-hydroperoxy cyclohexane, the emulsifying agent is potassium dehydroabietate and the activator is an electromotive couple having a standard oxidationreduction potential between about 0.8 and 0.5 volt.

9. The process of claim 1 wherein butadiene-1,3 and acrylonitrile are polymerized.

10. The process of claim 9 wherein the hydroperoxide is tricyclohexyl hydroperoxide, the emulsifying agent is potassium dehydroabietate and the activator is an electromotive couple having a standard oxidation-reduction potential between about -0.8 and 0.5 volt.

11. The process which comprises polymerizing an organic compound containing the CHg=C group at a temperature below about 10 C. in aqueous emulsion in the presence of an emulsifying agent, an electromotive couple having a standard oxidation-reduction potential between about 1.0 and about O.3 volt as activator and as catalyst a hydroperoxide selected from the group consisting of polycyclohexyl hydroperoxides of the structural forrnulas:

OOll oetd 10 where R, R1 and R2 are of the group consisting of H, X, X0, XzN, Cl and Br and X is a saturated lower alkyl group.

12. The process of claim 11 in which the hydroperoxide is l-cycloheXyl-l-hydroperoxy cyclohexane.

13. The process of claim 12 in which the emulsifying agent is potassium dehydroabietate.

14. The process of claim 13 in which the butadiene-1,3 and styrene are polymerized and the activator is an electromotive couple having a standard oxidation-reduction potential between about 0.8 and 0.5 volt.

15. The process of claim 14 in which the activator is a Fe++, Fe+++ electrornotive couple.

16. The process of claim 11 in which the hydroperoxide is tricyclohexyl hydroperoxide.

17. The process of claim 16 in which the emulsifying agent is potassium dehydroabietate.

18. The process of claim 17 in which butadiene-1,3 and styrene are polymerized and the activator is an electromotive couple having a standard oxidation-reduction potential between about -O.8 and 0.5 volt.

19. The process of claim 18 wherein the activator is a Fe++, Fe+++ electromotive couple.

Reynolds et al Aug. 12, 1952 Fryling et al Sept. 2, 1952 

1. THE PROCESS WHICH COMPRISES POLYMERIZING AN ORGANIC COMPOUND CONTAINING THE CH2=C<GROUP AT A TEMPERATURE BELOW ABOUT 10*C. IN AQUEOUS EMULSION IN THE PRESENCE O FAN EMULSIGYING AGENT, AN ELECTROMOTIVE COUPLE HAVING A STANDARD OXIDATION-REDUCTION POTENTIAL BETWEEN ABOUT - 1.0 AND ABOUT -0.3 VOLT AS ACTIVATE AND AS CATALYST A POLYCYCLOHEXYL HYDROPEROXIDE IN WHICH THE HYDROPEROXY GROUP IS ATTACHED TO A TERTIARY CARBON ATOM IN A CYCLOHEXYL RING. 